BTATz二聚体分子间相互作用的理论计算  

Theoretical Study on Intermolecular Interactions of 3,6-Bis(1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine Dimers

作　　者：胡银[1] 邵颖慧[1] 胡荣祖[1] 宋纪蓉[2,3] 马海霞[2] 

机构地区：[1]西安近代化学研究所,陕西西安710065 [2]西北大学化工学院/陕西省物理无机化学重点实验室,陕西西安710069 [3]故宫博物院文保科技部,北京100009

出　　处：《含能材料》2012年第3期273-279,共7页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金(20603026);陕西省自然科学基金(2009JQ2002)

摘　　要：在DFT-B3LYP/6-31G*水平下,求得3,6-双(1-氢-1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪(BTATz)二聚体势能面上6种优化几何构型和电子结构。经基组叠加误差(BSSE)和零点能(ZPE)校正,求得分子间最大相互作用能为-68.82 kJ.mol-1。由自然键轨道(NBO)分析揭示了分子间相互作用的本质。对优化构型进行振动分析,并基于统计热力学求得200.0～800.0 K温度范围从单体形成二聚体的热力学性质变化,发现二聚主要由强氢键所贡献。二聚过程在200.0～400.0 K均能自发进行。Six optimized stable 3,6-bis（1 H-1 ,2,3,4-tetrazol-5-yl-amino）-1,2,4,5-tetrazine （BTATz） dimers were found on the potential energy surface and their electronic structures have been obtained by using density functional theory （DFT） at the B3LYPI6-31 G＊ level. The largest corrected intermolecular interaction energy of the dimer calculated with basis set superposition error correction （BSSE） and zero point energy （ZPE） correction is -68.82 kJ · mol^-1. The natural bond orbital （NBO） analysis was performed to reveal the origin of the interaction. Based on the vibrational analysis,the changes of thermodynamic properties from the monomer to dimer with the temperature ranging from 200.0 K to 800.0 K have been obtained using the statistical thermodynamic method,founding that the strong hydrogen bonds dominantly contribute to the dimers. The dimerization process can occur spontaneously over the temperature from 200 K to 400 K.

关 键 词：物理化学 3 6-双(1-氢-1 2 3 4-四唑-5-氨基)-1 2 4 5-四嗪(BTATz) 分子间相互作用 密度泛函理论(DFT) 自然键轨道分析(NBO) 热力学性质 

分 类 号：O631.1[理学—高分子化学]